CN106745212A - A kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts - Google Patents
A kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts Download PDFInfo
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- CN106745212A CN106745212A CN201710014343.7A CN201710014343A CN106745212A CN 106745212 A CN106745212 A CN 106745212A CN 201710014343 A CN201710014343 A CN 201710014343A CN 106745212 A CN106745212 A CN 106745212A
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- carrier
- dimethyl oxalate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 239000000969 carrier Substances 0.000 title claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920000858 Cyclodextrin Polymers 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Chemical group 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Chemical group 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 229910017676 MgTiO3 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical group CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFNKLDDSWHOKLQ-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O OFNKLDDSWHOKLQ-UHFFFAOYSA-N 0.000 description 1
- 241000627951 Osteobrama cotio Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/613—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
Abstract
The invention discloses a kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts.Preparation method of the present invention is that soluble M salt (M salt is nitrate, chloride, the acetate of Zn, Mg, Ca and Co) is added in the glacial acetic acid solution of titanate esters, the organic matter for adding macromolecule is pore-foaming agent, it is stirred continuously in 60~90 DEG C of water-baths until formation clear gel, will prepare MTiO after the drying of this gel, roasting, extruded moulding3Carrier.The crystallinity of the carrier prepared using this method is high, with random laminated structure.The surface of carrier has the basic sites of varying strength, but main based on alkalescent.Prepared carrier specific surface area is 10~35m2/ g, its average pore size is 8~25nm.Carrier prepared by the method carrys out catalytic CO oxidative coupling synthesizing dimethyl oxalate suitable for preparing the Pd base catalyst of support type.
Description
Technical field
The present invention relates to a kind of preparation method of carrier, the carrier is mainly for the preparation of loading type Pd base catalyst one
Carbonoxide oxidative coupling synthesizing dimethyl oxalate, belongs to the preparing technical field of dimethyl oxalate.
Background technology
Carrier is the important component of solid catalyst, is the material for supporting active component and auxiliary agent.In catalysis
The effect of the carrier in reaction mainly has：(1) increase active surface and the suitable pore structure of offer；(2) machine of catalyst is improved
Tool intensity, it is ensured that it has certain shape；(3) thermal conductivity and heat endurance of catalyst are improved, in case hot-spot causes
The sintering deactivation of catalyst；(4) peptizaiton and supporting role are played to major catalyst.
Carbon monoxide gas-phase catalytic coupling synthesizing dimethyl oxalate is a committed step of coal-ethylene glycol technique.This is anti-
The quality of catalyst performance depends not only on the preparation method of catalyst needed for answering, and also depends on the selection to carrier.Mesh
It is preceding appeared in the newspapers in (104190414B, 104190415B, 102527377A, 102527377A, 105597743A,
105381799A etc.) synthesizing dimethyl oxalate catalyst is using α-Al2O3Make carrier, due to α-Al2O3It is high by 1300 DEG C
Temperature roasting, this will cause α-Al2O3Some ducts of carrier cave in during high-temperature roasting, so as to cause its specific surface
Product and average pore size diminish.Specific surface area is too small, is unfavorable for the dispersion of active component, so as to be unfavorable for the hair of catalyst activity
Wave.In order to overcome α-Al2O3The less specific surface area of carrier and less aperture, the invention discloses a kind of synthesis of oxalic acid two
Methyl esters catalyst MTiO3The preparation method of carrier, carrier crystallinity prepared by the method is high, in random laminated structure, its
Specific surface area and average pore size can be controlled by adding proper amount of pore-foaming agent.The carrier provided using the method is negative to prepare
The Pd base catalyst of load type, it shows preferably catalysis in the reaction of carbon monoxide gas phase coupling synthesizing dimethyl oxalate and lives
Property.In the case of relatively low Pd load capacity (0.3%, in terms of carrier quality), the space-time yield of dimethyl oxalate can reach
1200g/LcatMore than h, the selectivity of dimethyl oxalate can reach more than 98%.
The content of the invention
It is an object of the invention to provide a kind of carrier for synthesizing dimethyl oxalate catalyst.The load that this method is provided
Body is mainly used to prepare the Pd bases catalyst of support type to be catalyzed CO coupling synthesizing dimethyl oxalate reactions.
Provided by the present invention for synthesizing dimethyl oxalate catalyst MTiO3The preparation method of carrier, its preparation process
For：
A., titanate esters are dissolved in glacial acetic acid the solution for forming 0.5mol/L~1.5mol/L；The titanate esters are metatitanic acid four
Any one in N-butyl, tetrabutyl titanate, the n-propyl of metatitanic acid four, tetraisopropyl titanate；
B. by the salting liquid of soluble M salt formation 0.5mol/L~1.5mol/L soluble in water；Wherein M represents Mg2+、Ca2 +、Zn2+、Co2+、Ni2+In any one, anion in salting liquid is any one in nitrate anion, acetate, chlorion
Kind, preferably M salt is magnesium nitrate, calcium nitrate or cobalt nitrate；
C. the solution that step B is obtained is added in the solution of step A, while addition pore-foaming agent is in 60~90 DEG C of water-baths
It is stirred continuously, until forming clear gel；Wherein the addition of pore-foaming agent is the 1~10% of solution kind titanium quality；
Described pore-foaming agent is glucose, P123, cyclodextrin, polyethylene glycol, polyvinyl alcohol, PEO, shitosan
In any one, it is preferred that cyclodextrin, shitosan or polyethylene glycol；
D. above-mentioned gel is placed in baking oven and 12h is dried at 60~80 DEG C, then be warming up to 100~120 DEG C and dry 12h, most
After be placed in Muffle furnace 450~600 DEG C of 4~6h of roasting after obtain block white powder；
E. above-mentioned block white powder is carried out into ball milling, is subsequently adding the aqueous solution of polyvinyl alcohol as adhesive, passed through
After extruded moulding, required carrier is obtained after 700 DEG C of high-temperature roastings.
Prepared support chemistry formula is MTiO3, wherein M represents Mg2+、Ca2+、Zn2+、Co2+、Ni2+In any one,
Its specific surface area is 10~35m2/ g, equal aperture is 8~25nm.
Carrier to obtaining carries out characterization result and sees Fig. 1-5, and as seen from Figure 1, prepared carrier key component is
MgTiO3, but contain a small amount of MgO and TiO2.From Figure 2 it can be seen that prepared MgTiO3Carrier is random laminated structure.Figure
3 N2Adsorption desorption curve show that the hole of prepared carrier is mainly slit-type.The CO of Fig. 42Temperature programmed desorption curve
Show that prepared carrier surface has the basic sites of different intensity, but based on alkalescent, this alkalescent can have
Effect suppresses the catalytic decomposition of methyl nitrite.
The MTiO prepared with this method is can be seen that from the evaluation result of the catalyst of table 13 areCatalyst prepared by carrier,
During the load capacity of Pd as little as 0.3%, the selectivity of dimethyl oxalate is higher than 98%, and the yield of dimethyl oxalate can reach
1200g/LcatMore than h.
Beneficial effects of the present invention：The preparation technology for being used is unique, has no document report, prepared MTiO3Carrier
In random laminated structure, the crystallinity of carrier is high, and carrier surface is presented alkalescent, the specific surface area and average pore size of carrier
Can be controlled by adding different amounts of pore-foaming agent.The MTiO prepared using the inventive method3Carrier prepares oxalic acid diformazan
Catalyst for ester synthesis, its catalysis activity is good, and the decentralization of active component Pd is high, at the same dimethyl oxalate with selection higher
Property and space-time yield.
Brief description of the drawings
The XRD of carrier prepared by Fig. 1 embodiments 1.
The SEM figures of carrier prepared by Fig. 2 embodiments 1.
The N of carrier prepared by Fig. 3 embodiments 12Adsorption desorption curve map.
The CO of carrier prepared by Fig. 4 embodiments 12Temperature programmed desorption curve map.
The TEM spectrograms of the dimethyl oxalate synthetic catalyst that Fig. 5 is prepared using the carrier that embodiment 1 is obtained.
Specific embodiment
Below by specific embodiment to synthesis gas dimethyl oxalate catalyst MTiO of the invention3The preparation of carrier
Method is described in detail, but the present invention is not limited to specific examples below.
Embodiment 1
Weigh the positive ester of 0.02mol metatitanic acids four and be dissolved in glacial acetic acid, form the solution of 0.5mol/L.Weigh 0.02mol magnesium nitrates
The solution of formation 0.4mol/L in deionized water is dissolved in, the configured good positive fourth of metatitanic acid four is added under conditions of being stirred continuously
In the acetum of ester, while adding 0.02g cyclodextrin as pore-foaming agent.Above-mentioned mixed solution is placed in 80 DEG C of water-bath,
Obtain clear gel.Oven drying 12h by above-mentioned gel at 60 DEG C, then by temperature rise to 100 DEG C dry 12h after, be transferred to
600 DEG C of roasting 2h in Muffle furnace are placed in corundum crucible, block white powder is obtained.After above-mentioned white powder ball milling, add
The polyvinyl alcohol water solution of 5mL 1mol/L carries out extruded moulding as adhesive after being sufficiently mixed, and is finally placed in 700 DEG C of Muffles
After kiln roasting 2h, that is, obtain MgTiO3Carrier.
To the MgTiO for obtaining3Carrier characterization result is shown in Fig. 1-4
Embodiment 2
Weigh 0.04mol tetrabutyl titanates and be dissolved in glacial acetic acid, form the solution of 1mol/L.Weigh 0.04mol calcium nitrate
The solution of formation 0.8mol/L in deionized water is dissolved in, the configured good isobutyl of metatitanic acid four is added under conditions of being stirred continuously
In the acetum of ester, while adding 0.04g cyclodextrin as pore-foaming agent.Above-mentioned mixed solution is placed in 85 DEG C of water-bath,
Obtain clear gel.Oven drying 12h by above-mentioned gel at 70 DEG C, then by temperature rise to 110 DEG C dry 12h after, be transferred to
500 DEG C of roasting 4h in Muffle furnace are placed in corundum crucible, block white powder is obtained.After above-mentioned white powder ball milling, add
The polyvinyl alcohol water solution of 5mL 1.5mol/L carries out extruded moulding as adhesive after being sufficiently mixed, and is finally placed in 700 DEG C of horses
Not after kiln roasting 4h, that is, obtain CaTiO3Carrier.
Embodiment 3
Weigh the n-propyl of 0.02mol metatitanic acids four and be dissolved in glacial acetic acid, form the solution of 0.5mol/L.Weigh 0.02mol nitric acid
Cobalt is dissolved in the solution of formation 0.4mol/L in deionized water, and configured good metatitanic acid four is being added under conditions of being stirred continuously just
In the acetum of propyl ester, while adding 0.02g shitosans as pore-foaming agent.Above-mentioned mixed solution is placed in 75 DEG C of water-bath
In, obtain clear gel.Oven drying 12h by above-mentioned gel at 80 DEG C, then by temperature rise to 120 DEG C dry 12h after, transfer
600 DEG C of roasting 6h in Muffle furnace are placed in into corundum crucible, block black powder is obtained.After by above-mentioned black powder ball milling, plus
Enter the polyvinyl alcohol water solution of 5mL 2mol/L as adhesive, extruded moulding is carried out after being sufficiently mixed, be finally placed in 700 DEG C of horses
Not after kiln roasting 5h, that is, obtain CoTiO of the invention3Carrier.
Embodiment 4
Weigh the positive ester of 0.03mol metatitanic acids four and be dissolved in glacial acetic acid, form the solution of 1.5mol/L.Weigh 0.03mol magnesium nitrates
The solution of formation 0.6mol/L in deionized water is dissolved in, the configured good positive fourth of metatitanic acid four is added under conditions of being stirred continuously
In the acetum of ester, while adding 0.03g polyethylene glycol as pore-foaming agent.Above-mentioned mixed solution is placed in 80 DEG C of water-bath
In, obtain clear gel.Oven drying 12h by above-mentioned gel at 80 DEG C, then by temperature rise to 110 DEG C dry 12h after, transfer
600 DEG C of roasting 4h in Muffle furnace are placed in into corundum crucible, block white powder is obtained.After by above-mentioned white powder ball milling, plus
Enter the polyvinyl alcohol water solution of 5mL 1.5mol/L as adhesive, extruded moulding is carried out after being sufficiently mixed, be finally placed in 700 DEG C
After Muffle kiln roasting 2h, that is, obtain ZnTiO of the invention3Carrier.
Application examples
(1) preparation of catalyst：The carrier for weighing 5g embodiments 1-4 preparations is added separately to 30mL 0.005mol/L's
In the solution of chlorine palladium acid sodium, 0.3g polyvinylpyrrolidones and 0.3g citric acids are subsequently adding, after stirring 1h, add 0.2g and resist
Bad hematic acid, continues to stir 12 hours at room temperature, then filters, and is washed for several times with distilled water and ethanol respectively, and 60 are placed in after filtering
DEG C vacuum drying chamber in dry 12 hours, that is, obtain required catalyst sample, numbering is M-1, M-2, M-3, M-4 respectively.
Transmission electron microscope characterization result is carried out to catalyst sample M-1 and sees Fig. 5, as seen from Figure 5, active component Pd particles (figure
In white bright spot) be dispersed on carrier, its average grain diameter is 3.5nm or so.
(2) catalyst sample performance evaluation：The catalyst sample of 2mL 10-20 mesh is measured with graduated cylinder, loading internal diameter is
In the reaction tube of 10mm, 50mL/min N are passed through2, 30mL/min H2, 6h is reduced under the conditions of 350 DEG C.Treat temperature drop to 130 DEG C
When, then start to be passed through 50mL/min N2, 30mL/min CO, 20mL/min methyl nitrites are reacted, and air speed is 3000h-1,
The evaluation result of catalyst sample is listed in Table 1 below.
The evaluation result of the embodiment catalyst sample of table 1.
As it can be seen from table 1 the MTiO prepared using the inventive method3Catalyst is prepared as carrier, in the negative of Pd
During carrying capacity as little as 0.3%, the selectivity of dimethyl oxalate is higher than 98%, and the yield of dimethyl oxalate can reach 1200g/
LcatMore than h.
Claims (2)
1. a kind of preparation method of synthesizing dimethyl oxalate carriers for catalysts, concretely comprises the following steps：
A., titanate esters are dissolved in glacial acetic acid the solution for being configured to 0.5~1.5mol/L；The titanate esters be tetra-n-butyl titanate,
Any one in tetrabutyl titanate, the n-propyl of metatitanic acid four, tetraisopropyl titanate；
B. by the salting liquid of 0.5~1.5mol/L of soluble M salt formation soluble in water；Wherein M represents Mg2+、Ca2+、Zn2+、Co2+、
Ni2+In any one, anion in salting liquid is NO3 -、CH3COO-、Cl-In any one；
C. the solution that step B is obtained is added in the solution of step A, while adding pore-foaming agent continuous in 60~90 DEG C of water-baths
Stirring, until forming clear gel；Wherein the addition of pore-foaming agent is the 1~10% of solution kind titanium quality；
Described pore-foaming agent is in glucose, P123, cyclodextrin, polyethylene glycol, polyvinyl alcohol, PEO, shitosan
Any one；
D. above-mentioned gel is placed in baking oven and 12h is dried at 60~80 DEG C, then be warming up to 100~120 DEG C and dry 12h, then put
450~600 DEG C of 4~6h of roasting, obtain block white powder in Muffle furnace；
E. above-mentioned block white powder is carried out into ball milling, the aqueous solution of polyvinyl alcohol is subsequently adding as adhesive, by extrusion
After shaping, carrier is obtained after 700 DEG C of high-temperature roastings；The chemical formula of prepared carrier is MTiO3, wherein M represents Mg2+、Ca2 +、Zn2+、Co2+、Ni2+In any one, its specific surface area be 10~35m2/ g, equal aperture is 8~25nm.
2. the preparation method of synthesizing dimethyl oxalate carriers for catalysts according to claim 1, it is characterized in that：
M salt described in step B is magnesium nitrate, calcium nitrate or cobalt nitrate；
Pore-foaming agent described in step C is cyclodextrin, shitosan or polyethylene glycol；
The carrier MTiO that step E is obtained3Middle M is Mg2+、Ca2+、Co2+In any one.
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| CN111939929A (en) * | 2020-09-08 | 2020-11-17 | 安徽师范大学 | Binary metal nano Pd/alumina catalyst and preparation method thereof, and method for preparing dimethyl oxalate through CO coupling oxidation |
| CN114433081A (en) * | 2022-02-25 | 2022-05-06 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO-production of carbonic ester and formic ester by synthesizing oxalate with CO |
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